Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
  • B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
  • B01D61/027—Nanofiltration
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
  • C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
  • C07C45/50—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide by oxo-reactions
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
  • C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
  • C07C45/50—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide by oxo-reactions
  • C07C45/505—Asymmetric hydroformylation
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
  • C07C45/78—Separation; Purification; Stabilisation; Use of additives
  • C07C45/786—Separation; Purification; Stabilisation; Use of additives by membrane separation process, e.g. pervaporation, perstraction, reverse osmosis
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
  • C07C45/78—Separation; Purification; Stabilisation; Use of additives
  • C07C45/81—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
  • C07C45/82—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
  • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
  • C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
  • C07C51/23—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups
  • C07C51/235—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups of —CHO groups or primary alcohol groups
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
  • C07C51/42—Separation; Purification; Stabilisation; Use of additives
  • C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation

Definitions

• the present invention relates to a process for the preparation of a product mixture by technical hydroformylation of a hydrocarbon stream containing isobutene and to separating the product mixture obtained, as well as a device for the process according to the invention and the use of a device according to the invention.
• Hydroformylation in the technical field generally means the reaction of an olefin with synthesis gas (mainly consisting of carbon monoxide and hydrogen gas mixture), usually under pressure and in the presence of a transition metal complex catalyst, to an aldehyde extended by one carbon atom relative to the olefin.
• synthesis gas mainly consisting of carbon monoxide and hydrogen gas mixture
• the hydroformylation serves to produce higher aldehydes.
• Higher aldehydes in particular those having 3 to 25 carbon atoms, are used, for example, as synthesis precursors, for the preparation of carboxylic acids and as fragrances.
• they are often converted by catalytic hydrogenation into the corresponding alcohols, which in turn serve for the preparation of plasticizers and detergents.
• the oxo reaction is carried out on an industrial scale.
• isovaleraldehyde which is hereinafter referred to as 3-methylbutanal or short 3MBA.
• 3MBA is used to manufacture
• Odoriferous and aromatic substances and used as a synthesis precursor.
• organophosphorus metal complex catalysts based on cobalt or rhodium are used today.
• the catalysts are dissolved homogeneously in the liquid hydroformylation mixture.
• the homogeneous catalyst from the hydroformylation mixture must also be removed gently, since the complex catalyst reacts relatively sensitively to changes in state and could lose its activity.
• the catalyst is removed by distillation from the hydroformylation mixture.
• efforts have recently been made to separate the homogeneously dissolved catalyst from the hydroformylation mixture by means of membrane technology (nanofiltration).
• EP1931472B1 is generally concerned with organophilic nanofiltration for the separation of homogeneously dissolved catalyst complexes from hydroformylation mixtures.
• the catalyzed hydroformylation of olefins to the corresponding aldehydes is usually carried out in a homogeneous, liquid phase, ie catalyst, olefin and products are present in one phase, wherein the transition metal complex catalyst is homogeneously dissolved in the liquid reaction mixture, which is also the olefin to be hydroformylated and products of Hydroformylation.
• the transition metal complex catalyst is homogeneously dissolved in the liquid reaction mixture, which is also the olefin to be hydroformylated and products of Hydroformylation.
• products of the hydroformylation in addition to the said aldehyde as the primary product 3-methylbutanal, typically also higher-boiling secondary products (usually referred to as high-boiling components) are formed.
• an inert solvent may be present in the reaction mixture for the transition metal complex catalyst, such as, for example, dioctyl phthalate or diisononyl phthalate or isononyl benzoate or mixtures thereof.
• high boilers are meant substances which boil at a higher temperature and have higher molecular weights than the primary hydroformylation product (aldehyde having one carbon atom more than the olefin used) and the alcohol obtained therefrom by hydrogenation
• Typical high hydroformylation hydroformylation products include aldolization products and acetalization products as well as esters formed by reaction of alcohols and acids, the alcohols and acids being formed in particular by disproportionation of aldehydes.
• the industrial hydroformylation of isobutene typically produces a product mixture which comprises, in addition to the primary product 3-methylbutanal, which is the target product of the industrial hydroformylation of isobutene, secondary products in the form of high boilers and the transition metal complex catalyst and its free ligands.
• the product mixture removed from the reactor may also contain unreacted educt, ie isobutene, hydrogen or carbon monoxide.
• a method of enriching a homogeneous catalyst from a process stream is known from WO2010097376A1.
• the process stream originates, for example, from a process for the hydroformylation of olefins, preferably having 2 to 25 carbon atoms, to the corresponding aldehydes, in particular isononanal and isotridecanal.
• the enrichment of the homogeneous catalyst from the process stream is carried out in such a way that the process stream is passed over at least one nanofiltration membrane which consists wholly or partly of a polymer having planar polymer units which are interconnected via a rigid linker, wherein the linker in is twisted so that at least one planar polymer unit is connected via the linker in a non-coplanar arrangement to at least one second planar polymer unit.
• the catalyst system remains in the retentate while the high boilers are separated with the permeate.
• separation by membrane filtration is preferably carried out by distillation separation of the discharge of the hydroformylation in a distillate, the unreacted olefins and the containing desired aldehydes, and a bottom product containing high boilers and the catalyst system.
• WO2010097428 Another method for separating and partially recycling a transition metal complex catalyst from a reaction mixture, e.g. from the reaction mixture obtained in a technical hydroformylation is known from WO2010097428.
• This method is based on a combination of at least single-stage membrane separation and adsorption.
• a catalyst-containing stream is separated via at least one single-stage membrane separation step into a retentate stream enriched in transition metal complex catalyst and a permeate stream depleted in transition metal complex catalyst.
• the retentate stream enriched in transition metal complex catalyst is recycled to the reactor.
• the permeate stream depleted in transition metal complex catalyst is fed to an adsorption step in which further separation of the transition metal complex catalyst from the permeate stream takes place.
• the object of the present invention is thus to provide a method and an apparatus for producing a product mixture by technical hydroformylation of a hydrocarbon stream containing isobutene and for separating the resulting product mixture, which make it possible to minimize the proportion of high boilers in the product mixture and thus the Increase the yield of the reaction.
• the aldol condensate can be reduced to a dihydric Cio alcohol by reaction with the primary product 3-methylbutanal, the primary product 3-methylbutanal being used to
• the solution according to the invention of the abovementioned object of keeping the proportion of high boilers in the resulting product mixture of the hydroformylation as low as possible consists primarily of separating off 3-methylbutanoic acid as far as possible from the transition metal complex catalyst attributable to the hydroformylation reactor , This can be achieved by enriching in the resulting hydroformylation product hydroformylation step the transition metal complex catalyst in the resulting nanofiltration retentate, while the secondary products of the hydroformylation reaction, in particular 3MBS, are enriched in the resulting permeate of the nanofiltration device.
• nanofiltration ie. H.
• a nanofiltration device is used for the nanofiltration T renn Whitney of the inventive method, which contains one or more nanofiltration membranes, which are characterized by a particularly low retention for 3-methylbutanoic acid.
• the retention of the nanofiltration membrane for 3-methylbutanoic acid is -1 or smaller, more preferably -5 or smaller, and most preferably -10 or smaller. The definition of the retention of a membrane can be found below.
• the 3-methylbutanoic acid discharged in the reactor with the permeate of the nanofiltration device is no longer available as a reaction partner for the high boiler formation, meaning that important reactions involved in the high-boiling formation no longer or only to a lesser extent expire. This reduces the loss relative to the primary product 3-methylbutanal.
• An important aspect of the teaching according to the invention is therefore the use of a nanofiltration device for separating the catalyst complex from the product mixture, which has a particularly high permeability to 3-methylbutanoic acid.
• a nanofiltration apparatus is understood to be a separation apparatus which performs its separation task exclusively with the aid of membranes, at least one of the membranes being a nanofiltration membrane.
• the nanofiltration device may comprise one or more membrane separation stages, accordingly, the nanofiltration device may operate in one or more stages.
• Each membrane separation stage has three connections, one feed and two processes, namely retentate and permeate.
• the resulting permeate or the resulting retentate is understood to mean the two processes of the nanofiltration device at their interfaces to the other components of the device for carrying out the method according to the invention. If the nanofiltration device operates only in one stage, and thus has only one membrane separation stage, the resulting permeate or the resulting retentate of the nanofiltration device corresponds to the permeate or the retentate of the single membrane separation stage.
• Nanofiltration is a pressure-driven membrane separation process.
• the molecular weight cut-off (MWCO), see YH See Toh, XX Loh, A. Bismarck, AG Livingston, In search of a standard method for the characterization of organic solvent nanofiltration membraenes, J Membr. Sei, 291 (2007) 120-125]) ranges from 150 g / mol to 2000 g / mol. This value can be used to distinguish the nanofiltarion from other membrane separation processes such as microfiltration and ultrafiltration.
• the cut-off is defined as the molecular weight of a preferred inert indicator system (eg, polystyrene standards or alkane standards in Toh, Loh, Bismarck and Livingston) in which a membrane has a 90% retention.
• a preferred inert indicator system eg, polystyrene standards or alkane standards in Toh, Loh, Bismarck and Livingston
• Nanofiltration membranes are characterized by a low retention of low molecular weight organic substances.
• the retention R of a membrane is determined by the local concentrations of a component i of the non-permeating stream (retentate) and of the permeating current through the membrane (permeate). If retentate and permeate are ideally mixed along the membrane, then the local retentate and permeate concentrations correspond to the respective concentration of the total amount of retentate or permeate.
• the retention R of a membrane for a component i contained in the feed stream is defined as follows:
• c Pi is the concentration of component i in the permeate P and c Ri is the concentration of component i in the retentate R.
• a preferred permeation of the component i is c Pi > c Ri , and R ⁇ 0.
• the nanofiltration device to be used in the method according to the invention comprises one or more nanofiltration membranes, wherein the or at least one of the nanofiltration membranes has a retention for 3-methylbutanoic acid of -1 or smaller, more preferably -5 or smaller, and especially -10 or smaller.
• a substantial removal of the 3-methylbutanoic acid from the resulting product mixture of the hydroformylation can be achieved, which is supplied to the nanofiltration device as an inlet.
• membranes comprising a release-active layer of a material selected from cellulose acetate, cellulose triacetate, cellulose nitrate, regenerated cellulose, polyimides, polyamides, polyetheretherketones, sulphonated polyetheretherketones, aromatic polyamides, polyamideimides, polybenzimidazoles, polybenzimidazolones, polyacrylonitrile, Polyarylethersulfones, polyesters, polycarbonates, polytetrafluoroethylene, polyvinylidene fluoride, polypropylene, polydimethylsiloxane, silicones, polyphosphazenes, polyphenylsulfides, polybenzimidazoles, 6.6 nylon, polysulfones, polyanilines, polyurethanes, acrylonitrile / glycidyl methacrylate (PANGMA), polytrimethylsilylpropyne, polymethylpentyne, polyvinylidene n
• membranes which have as a release-active layer a polymer layer of polydimethylsiloxane, polyimide, polyamideimide, acrylonitrile / glycidyl methacrylate (PANGMA), polyamide or polyetheretherketone, which are composed of polymers with intrinsic microporosity (PIM) such as PIM-1, or wherein the separation-active Layer is constructed over a hydrophobic ceramic membrane.
• PIM intrinsic microporosity
• membranes of silicones or polyamide-imide are commercially available.
• nanofiltration membranes comprising one or more polymers containing imide groups or consisting of one or more polymers containing imide groups are particularly suitable for the discharge of the 3-methylbutanoic acid from the product mixture of the hydroformylation, which is fed to the nanofiltration device as feed.
• Representatives of this class of membranes are in particular membranes made of polyimide or polyamide-imide.
• the thermoplastic polyimide can be used, which is available under the brand name Matrimid® from Huntsman Advanced Materials GmbH, Basel (Switzerland).
• Nanofiltration membranes made of polyimide or polyamide-imide are characterized by a particularly low retention of 3-methylbutanoic acid.
• nanofiltration membranes comprising or consisting of one or more polymers containing imide groups are preferably used in the nanofiltration device, wherein the polymer (s) or imide groups are selected such that the retention of the nanofiltration membrane for 3-methylbutanoic acid -1 or less is preferred -5 or smaller, and more preferably -10 or less.
• Nanofiltration membranes containing imide groups are commercially available, e.g. Under the product names STARMEM® 122 and 240 by WR Grace & Co.-Conn. 7500 Grace Drive Columbia, Md 21044 US or membranes of the product families Puramem® and Duremembran® available from Evonik Industries AG, Essen (Germany). Puramem® and Duramem® contain polyimides such as P84 and / or Matrimid 5218.
• the nanofiltration treatment to be used in the method according to the invention comprises one or more nanofiltration membranes, wherein the or at least one of the nanofiltration membranes has a separation limit in the range of 150 to 2000 g / mol, preferably 200 to 600 g / mol, particularly preferably 350 to 500.
• a nanofiltration membrane whose separation limit is higher than the molecular weight of 3-methylbutanoic acid (102 g / mol) is preferably used according to the invention.
• the separation limit is preferably above the molecular weight of the high boilers (200 to 350 g / mol) but below the catalyst (500 to 1000g / mol).
• nanofiltration membranes comprising or consisting of one or more polymers containing imide groups in a nanofiltration furnishing to be used in the process according to the invention, the polymer or imide group-containing polymers being selected such that the separation limit of the nanofiltration membrane is in the range from 150 to 2,000 g / mol is located.
• the temperature is the transmembrane pressure, the Reyonlds number at the nanofiltration membrane overflow, and the partial pressure of carbon monoxide and / or hydrogen.
• resulting reaction mixture is preferably first cooled, if this is necessary for reasons of membrane stability or for adjusting the separation limit, and relaxed, preferably to a pressure of about 200 kPa. In this case, volatile constituents such as unreacted isobutene or hydrogen and carbon monoxide are partially removed and possibly recycled.
• a high-pressure pump is supplied to those for the nanofiltration process necessary transmembrane pressure generated.
• the high-pressure pump can be preceded by a prefilter system.
• the nanofiltration device may comprise a plurality of separation stages in the form of (serial or parallel) membrane modules, wherein after each separation stage, the respective obtained permeate is fed as feed to the next separation stage, and the permeate from the last separation stage is fed to the thermal separation.
• Each separation step comprises at least one membrane module, each membrane module comprising a single or several nanofiltration membranes.
• a person skilled in the art understands a membrane module to be a practically manageable, application-specific arrangement of the membrane in an assembly.
• the thermal separation of the permeate following the step of separation in a nanofiltration plant in the process according to the invention typically comprises a distillation or thin-film evaporator or falling-film evaporator or a combination thereof in which the first fraction is obtained as top product and the second fraction as bottom product.
• further separation of the second fraction of the thermal separation by means of a nanofiltration device is not required.
• reaction mixture is understood to mean the entire mixture present in the hydroformylation reactor comprising the reactants (isobutene and synthesis gas), the primary product of the hydroformylation (3-methylbutanal), secondary products formed therefrom (3-methylbutanoic acid and high boilers) and the transition metal complex catalyst. From this reaction mixture is obtained by hydroformylation of the reactant isobutene, optionally after separation unreacted isobutene, the resulting product mixture to be separated by nanofiltration comprising at least 3-methylbutanal, secondary products in the form of high boilers and 3-methylbutanoic acid and the transition metal complex catalyst and its free ligands.
• unreacted starting materials are not separated from the reactor discharge before the nanofiltration device, these are part of the product mixture driven into the feed of the nanofiltration device.
• a complete conversion of isobutene is desired, but can not always be achieved in industrial practice. Usual conversion rates are over 95% by weight.
• Unreacted isobutene is separated either immediately before the nanofiltration device so that its feed is nearly isobutene-free.
• the educt carbon monoxide should preferably also be present in the feed, permeate and retentate of the nanofiltration device in order to stabilize the catalyst complex.
• one or more process parameters are adjusted in the hydroformylation step of the isobutene-containing hydrocarbon stream in such a way that the total concentration of secondary products in the form of high boilers and 3-methylbutanoic acid, based on the product mixture, ie the reactor effluent, is 30% by weight. % or less, wherein the parameter (s) to be set are preferably selected from the group consisting of pressure, temperature, mean residence time of the reaction mixture in the hydroformylation reactor, composition of the synthesis gas, concentration of the transition metal and transition metal-ligand ratio of the transition metal complex catalyst.
• the average residence time of the reaction mixture in the hydroformylation reactor By reducing the average residence time of the reaction mixture in the hydroformylation reactor, the time available for the undesirable secondary reactions can be reduced, but the average residence time, on the other hand, must be sufficiently high to permit an economically feasible degree of conversion of the starting materials.
• the average residence time can be influenced, for example, by the design of the length of the reactor.
• the temperature in the hydroformylation reactor By reducing the temperature in the hydroformylation reactor, the speed of the undesired secondary reactions can be reduced, but the temperature, on the other hand, must be high enough to allow an economically feasible degree of conversion of the educts.
• one or more process parameters are preferably adjusted so that the concentration of 3-methylbutanoic acid in the product mixture to be supplied in the nano-filtration device is in the range between 0.004 and 0.1% by weight. is, preferably in the range between 0.004 and 0.03 wt%.
• the concentration of the catalyst complex in the resulting permeate is preferably 0.03% by weight or less.
• the step of hydroformylating the isobutene-containing hydrocarbon stream is preferably carried out at a pressure in the range from 0.2 to 8.0 MPa,
• transition metal complex catalyst whose transition metal is rhodium and / or whose ligand or its ligands are selected from the group of the organophosphorus ligands. It is also possible to use a transition metal complex catalyst whose transition metal is cobalt.
• the temperature in the hydroformylation reactor does not exceed 130 ° C.
• the hydroformylation is carried out at a temperature in the range of 80 to 1 10 ° C.
• a preferred method according to the invention comprises the steps
• Suitable methods for monitoring the concentration of 3-methylbutanoic acid in the retentate of the nanofiltration device, and preferably also in the resulting product mixture of the hydroformylation and / or in the feed and / or in the permeate of the nanofiltration device comprise a measurement of the concentration of 3-methylbutanoic acid in the respective process stream with a measurement method selected from the group consisting of gas chromatography.
• An increase in the concentration of 3-methylbutanoic acid in the retentate of the nanofiltration device could indicate a blockage of the nanofiltration membrane by deposits (membrane fouling).
• the recycling of the retentate into the hydroformylation reactor is interrupted. As a result, it is possible to prevent the concentration of 3-methylbutanoic acid in the hydroformylation reactor from increasing, thus promoting the undesired formation of high boilers.
• a sudden increase in the concentration of 3-methyl butyric acid in the inlet of the nanofiltration device could even be Evidence of failure or out-of-control devices controlling one or more hydroformylation process parameters.
• this described variant of the method according to the invention can contribute to the safe control of the process parameters of the hydroformylation, and possibly even to avoid defective production and operational disturbances.
• one or more process parameters of the step of hydroformylating the isobutene-containing hydrocarbon stream in the hydroformylation reactor are modified so that the concentration of 3-methylbutanoic acid in the feed the nanofiltration level is lowered to or below the specified maximum value.
• the suitable adjustment of one or more process parameters of the hydroformylation is preferably carried out as described above, wherein the parameters to be adjusted are in particular selected from the group consisting of pressure, temperature, mean residence time of the reaction mixture in the hydroformylation reactor, composition of the synthesis gas, concentration of the transition metal and transition metal ligand. Ratio of transition metal complex catalyst.
• the present invention additionally relates to a device for carrying out the method according to the invention, in particular for the preferred variants of the method according to the invention described above.
• An apparatus for carrying out the method according to the invention comprises:
• a nanofiltration device (M) comprising one or more membrane separation stages for separating the product mixture (2) formed in the hydroformylation reactor (R), so that in the resulting retentate (3) of the nanofiltration device (M) the transition metal complex catalyst and its free ligands relative to the 3-methylbutanal and the 3-methylbutanoic acid are enriched, and in the resulting permeate of the nanofiltration device (M) 3-methylbutanal and 3-methylbutanoic acid are enriched in the transition metal complex catalyst, such that the concentration of the 3-methylbutanoic acid in the resulting retentate (3) is lower as in the resulting permeate (4), wherein the nanofiltration device (M) comprises one or more nanofiltration membranes, wherein the or at least one of the nanofiltration membranes has a retention for 3-methylbutanoic acid of -1 or smaller, more preferably -5 or smaller, and especially -10 or smaller,
• At least one thermal separator (D) for thermally separating the resulting permeate (4) of the nanofiltration device (M) into a first fraction (5) and a second fraction (6), the first fraction (5) having a higher concentration of 3-methylbutanal contains as the second fraction (6) and a lower concentration of secondary products in the form of high boilers and 3-methyl butyric acid as the second fraction (6), Means for returning at least a partial stream of the resulting retentate (3) of the nanofiltration device (M) in the hydroformylation reactor (R).
• the apparatus for carrying out the method according to the invention may also contain conventional ingredients commonly used in the art, e.g. Pumps, conventional dosing, measuring, control and regulating devices, heating and cooling devices, etc.
• Pumps e.g. Pumps, conventional dosing, measuring, control and regulating devices, heating and cooling devices, etc.
• Such belonging to the prior art and common in chemical engineering components of devices for technical synthesis and separation methods are known in the art.
• an apparatus is preferably used from the group consisting of stirred tank, bubble column, jet nozzle reactor, tubular reactor and Schaufen reactor, the apparatus may be provided with internals.
• the hydroformylation reactor is designed as a bubble column reactor.
• the length expansion of the hydroformylation reactor is preferably selected such that a residence time of the reaction mixture in the hydroformylation reactor results which is sufficient for an economically reasonable degree of conversion of the starting materials to the primary hydroformylation product 3-methylbutanal, but not a high degree Reaction of the primary hydroformylation product 3-methylbutanal to yield products in the form of 3-methylbutanoic acid and high boilers allowed.
• the nanofiltration device of the device according to the invention preferably comprises one or more membrane modules.
• the nanofiltration membranes are arranged so that the retentate side of the nanofiltration membrane can be overflowed so that the concentration polarization of the separated components, ie the transition metal complex catalyst, counteracted and also the necessary driving force (pressure) can be impressed.
• the permeate is combined in the permeate collection space on the permeate side of the nanofiltration membranes and removed from the module.
• Common membrane modules have the nanofiltration membranes in the form of membrane discs, membrane pads or membrane pockets.
• membrane modules with open-channel cushion module systems in which the nanofiltration membranes are thermally welded or glued to membrane pockets or pillows, or wound modules in which the nanofiltration are glued or welded on membranes to membrane pockets or membrane pads and wound with feed spacers around a Permeatsammelrohr.
• the nanofiltration device of the device according to the invention is designed such that the preferred process parameters described above from the group consisting of pressure, temperature, average residence time of the reaction mixture in the hydroformylation reactor, composition of the synthesis gas, concentration of transition metal and transition metal-ligand ratio of Have transition metal complex catalyst set and / or the above-described preferred variants of carrying out the step of separating the resulting product mixture of the hydroformylation can be realized.
• the nanofiltration device may comprise a plurality of separation stages, which are arranged such that after each separation stage the resulting permeate is fed in each case as feed to the next separation stage, and the permeate from the last separation stage is supplied to the thermal separation.
• Each separation stage may be designed as a membrane module or comprise a plurality of membrane modules arranged in parallel.
• Each membrane module may comprise one or more nanofiltration membranes arranged in parallel.
• the nanofiltration device comprises one or more nanofiltration membranes, wherein the or at least one of the nanofiltration membranes has a cut-off in the range of 150 to 2000 g / mol, preferably 200 to 600 g / mol and particularly preferably 350 to 500 g / mol.
• the device according to the invention additionally comprises a device for determining the concentration of 3-methylbutanoic acid in the retentate of the nanofiltration device preferably additionally comprises a device for determining the concentration of 3-methylbutanoic acid in the resulting product mixture of the hydroformylation and / or in the feed of the nanofiltration device and / or a device for determining the concentration of 3-methylbutanoic acid in the permeate of the nanofiltration device,
• a device for taking samples of the retentate of the nanofiltration device preferably additionally a device for taking samples from the resulting product mixture of the hydroformylation and / or from the inlet of the nanofiltration device and / or a device for taking samples from the permeate of the nanofiltration device.
• the device for determining the concentration of 3-methylbutanoic acid in the inlet of the nanofiltration device is preferably selected from the group consisting of gas chromatographs. The same applies to the optionally provided devices for determining the concentration of 3-methylbutanoic acid in the retentate and / or permeate of the nanofiltration device.
• the concentration of 3-methylbutanoic acid in the resulting product mixture of the hydroformylation and / or feed and / or retentate and / or permeate of the nanofiltration device are not possible or too complicated.
• devices for taking samples from the resulting product mixture of the hydroformylation, the feed and / or retentate and / or permeate of the nanofiltration device are provided.
• the concentration of 3-methylbutanoic acid is determined, for example, in a process control laboratory.
• the present invention further encompasses the use of a device according to the invention, in particular in its preferred embodiments, for producing a product mixture by technical hydroformylation of a hydrocarbon stream containing isobutene and for separating the resulting product mixture, in particular by a process according to one of the preferred variants of the inventive process described above.
• Fig. 1 Apparatus for producing a product mixture by technical
• Fig. 2 Graphical 3MBS concentrations in the feed, retentate and
• FIG. 3 Graphic representation of the 3MBS retention of nanofiltration.
• FIG. 1 To produce a product mixture by technical hydroformylation of a hydrocarbon stream containing isobutene 1 and to separate the product mixture 2 obtained, a device shown in FIG. 1 comprising a hydroformylation reactor R in the form of a bubble column, a nanofiltration device M and a distillation device D is used. Sampling devices P are provided in the device which make it possible to take samples from the product stream 2 leaving the reactor R at certain intervals and from the retentate 3 and the permeate 4 of the nanofiltration device M.
• the nanofiltration device M comprises a membrane module in the form of a wound module.
• the nanofiltration membrane is a STARMEM 122 membrane from W.R. Grace & Co. and contains polyimide P84.
• the hydroformylation reactor R is fed with a hydrocarbon stream 1 comprising isobutene and synthesis gas.
• the hydroformylation of the isobutene is carried out to 3-methylbutanal at a pressure in the range of 0.2 to 8.0 MPa and a temperature in the range of 70 to 130 ° C with a mean residence time in the range of 1 to 4 hours, one Synthesis gas composition (CO / H2) of 1: 3 to 3: 1, a rhodium concentration in the range of 20 to 100 ppm and a rhodium-ligand ratio in the range of 1: 4 to 1: 50.
• CO / H2 Synthesis gas composition
• the resulting product mixture 2 of the hydroformylation in which the concentration of 3-methylbutanoic acid is in the range between 0.01 and 0.04% by weight, is then in a nanofiltration M at a temperature in the range of 30 to 35 ° C, a trans Membrane pressure in the range of 3.1 to 3.8 MPa and a carbon monoxide partial pressure in the range of 0.9 to 1, 2 MPa separated.
• the nanofiltration device M is designed in such a way that the Reynolds number is between 170 and 900 when the nanofiltration membrane overflows.
• a resulting retentate 3 and a resulting permeate 4 are removed.
• the ratio of product mixture 2 supplied to the membrane - also referred to as feed - and permeate 4 was adjusted to 0.82.
• the retentate stream 3, in which the transition metal complex catalyst is enriched, is recycled to the reactor R. From the product mixture 2 leaving the reactor R, the retentate 3 and the permeate 4 samples are taken at regular intervals with sampling devices P to determine the concentration of 3-methylbutanoic acid in the respective stream.
• the resulting permeate 4 of the nanofiltration device M in which the primary hydroformylation product 3-methylbutanal and 3-methylbutanoic acid are enriched, is separated by distillation in a thermal separation device in the form of a distillation unit D into a first fraction 5 and a second fraction 6.
• the concentration of 3-methylbutanal is higher than in the second fraction 6 and the concentration of 3-methylbutanoic acid and high boilers less than in the second fraction.
• FIG. 2 shows the 3MBS concentration in the feed, retentate and permeate of nanofiltration M over a period of 500 hours.
• FIG. 3 clearly shows negative retention of the Starmem 122 membrane used for the 3 MBS in the nanofiltration step. The retention is defined as 1 - (concentration permeate) / (concentration retentate).

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